CN1583562A - Double microporous zeolite molecular sieves and preparing method thereof - Google Patents
Double microporous zeolite molecular sieves and preparing method thereof Download PDFInfo
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- CN1583562A CN1583562A CN 200410012333 CN200410012333A CN1583562A CN 1583562 A CN1583562 A CN 1583562A CN 200410012333 CN200410012333 CN 200410012333 CN 200410012333 A CN200410012333 A CN 200410012333A CN 1583562 A CN1583562 A CN 1583562A
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- 239000010457 zeolite Substances 0.000 title claims abstract description 76
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 60
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 24
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012153 distilled water Substances 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 238000002425 crystallisation Methods 0.000 claims description 21
- 230000008025 crystallization Effects 0.000 claims description 21
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 20
- 229910001220 stainless steel Inorganic materials 0.000 claims description 20
- 239000010935 stainless steel Substances 0.000 claims description 20
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 claims description 12
- 235000015110 jellies Nutrition 0.000 claims description 11
- 239000008274 jelly Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000003921 oil Substances 0.000 claims description 11
- 239000006228 supernatant Substances 0.000 claims description 11
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 238000009991 scouring Methods 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000004115 Sodium Silicate Substances 0.000 abstract description 9
- 229910052911 sodium silicate Inorganic materials 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000012847 fine chemical Substances 0.000 abstract description 4
- 238000001308 synthesis method Methods 0.000 abstract description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 abstract 1
- 238000012856 packing Methods 0.000 description 16
- 238000002441 X-ray diffraction Methods 0.000 description 9
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 8
- 229910001388 sodium aluminate Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- GDEQPEBFOWYWSA-UHFFFAOYSA-N 1,2-dimethyl-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(C)=C1C GDEQPEBFOWYWSA-UHFFFAOYSA-N 0.000 description 1
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
一种双微孔沸石分子筛及制备方法，属于精细化工领域，具体涉及一种复合分子筛的制备方法。其特征在于采用有序合成法，先利用硅酸钠、硅溶胶、偏铝酸钠、蒸馏水、氢氧化钠、浓硫酸为原料，按一定的物料配比初步合成出Y型沸石；后将其与溶有氨水的四乙基溴化胺溶液混合，最后再加入一定量的硅溶胶充分搅拌使之均匀，于130℃－140℃下晶化4－7天，洗涤烘干焙烧除去模板剂，最后得到具有Y/β双微孔结构的复合沸石分子筛。该方法制得的双微孔分子筛降低了β分子筛的合成成本，且酸性、水热稳定性等都有所提高，也可改善其催化性能，将在精细化工、石油化工等方面有潜在的应用前景。
A double microporous zeolite molecular sieve and a preparation method thereof belong to the field of fine chemical industry, and specifically relate to a preparation method of a composite molecular sieve. It is characterized in that it adopts an orderly synthesis method, first using sodium silicate, silica sol, sodium metaaluminate, distilled water, sodium hydroxide, and concentrated sulfuric acid as raw materials, and preliminarily synthesizes Y-type zeolite according to a certain material ratio; Mix with tetraethylammonium bromide solution dissolved in ammonia water, and finally add a certain amount of silica sol and stir well to make it uniform, crystallize at 130°C-140°C for 4-7 days, wash, dry and roast to remove the template agent, Finally, a composite zeolite molecular sieve with Y/β double microporous structure is obtained. The double microporous molecular sieve prepared by this method reduces the synthesis cost of β molecular sieve, and has improved acidity, hydrothermal stability, etc., and can also improve its catalytic performance. It will have potential applications in fine chemical industry, petrochemical industry, etc. prospect.
Description
One, technical field
Double-micropore zeolites molecular sieve of the present invention and preparation method are about the preparation method of a kind of inorganic hole catalytic material, belong to field of fine chemical, more particularly, are the preparation methods about the two micropore composite zeolite molecular sieves of a kind of Y/ β.
Two, technical background
Y-type zeolite is connected mutually along three crystalline axis direction by twelve-ring by octahedral zeolite cage and forms, and is a kind of good catalyzer, and not only cracking activity height, and selectivity is good.Utilizing REY to substitute the amorphous silicon aluminium microballoon rises gasoline output as catalyzer significantly.The production of USY zeolite has been satisfied and is carried out white gasoline in the world and keep high-octane requirement.Therefore the invention of y-type zeolite has epoch making significance in the catalytic cracking field.
The β zeolite is synthetic first in 1967 by Mobil company, owing to fail to solve its structure determination problem for a long time, the ZSM series zeolite synthesizes and successful Application in addition, therefore fail to cause enough attention of people, disclosed its distinctive Three Dimensions Structure until 1988, the β zeolite causes people's interest heavily again, it has good heat and hydrothermal stability, acidity and the acid acceptance and the hydrophobicity of appropriateness, and be unique macropore supersiliceous zeolite with intersection twelve-ring channel system, its catalytic applications shows the characteristics that hydrocarbon reaction is difficult for coking and long service life, at hydrocarbons hydrogenation cracking, hydroisomerization, alkane aromatization, aspect such as alkylation and transalkylation reaction shows excellent catalytic performance, is crucial catalytic material.H β zeolite is the catalyzer that a kind of good alternative Amberlyst-15 prepares MTBE.In the gas phase system, the activity that not only makes the H beta-zeolite catalyst has improved three times, and the while has also effectively reduced the loss of active ingredient, suppressed SO42-to the corrosion of equipment with to pollution (the F.Collingnon and G.Poncelet of environment, Stud.Surf.Sci.Catal., 135 (2001)) environment friendly that, has shown H β zeolite.In addition, H β zeolite shows very high activity in the reaction of dimethylbenzene isopropylation generation dimethyl cumene, selectivity and stability (C.R Patra, S.Kartikeyan and R.Kumar, Stud.Surf.Sci.Catal., 135 (2001)), the wherein active 80-90% that reaches theoretical value, selectivity reaches 90-99%.Particularly people such as Davis has synthesized chirality β zeolite (M.E.Davis, Chem.Mater., 4 (1992) 756.) by adding structure chirality directed agents, and this is unique zeolite molecular sieve with chiral structure of finding at present.Find that by the optical activity experiment institute's synthetic β zeolite can make 5% R, R-phenylbenzene glycol, this just shows that this zeolite has great potential using value.
Above-mentioned y-type zeolite and the β zeolite of showing all has important purposes at petrochemical industry.If can successfully prepare the matrix material of y-type zeolite and β zeolite, organically combine the characteristics of the two, will great application prospect be arranged in petrochemical complex and field of fine chemical.This is because prepared matrix material not only has the performance of y-type zeolite, also has simultaneously the performance of β zeolite, thereby polystep reaction is carried out simultaneously in a reactor, not only can reduce cost greatly, and because the existence of double-pore structure, acidity, hydrothermal stability and to water absorption can mediation, can improve catalytic performance.
Three, summary of the invention
Double-micropore zeolites molecular sieve of the present invention and preparation method's purpose is the advantage that organically combines y-type zeolite and β zeolite, and two micropore composite zeolite molecular sieves of a kind of Y/ of having β and preparation method are provided.The two micro porous molecular sieves that make all increase at aspects such as acidity, heat and hydrothermal stabilities, will the potential application prospect be arranged at aspects such as fine chemistry industry, petrochemical compleies.
Two micropore composite zeolite molecular sieves of the Y/ β that double-micropore zeolites molecular sieve of the present invention and preparation method provide and preparation method, mainly be to adopt orderly synthesis method, utilize water glass earlier, sodium metaaluminate, distilled water, sodium hydroxide, the vitriol oil are raw material, tentatively synthesize y-type zeolite by certain material proportion under certain temperature and time; After an amount of tetraethyl-amine bromide be dissolved in use distilled water, and add certain ammoniacal liquor, first synthetic sample leached mix with it behind the supernatant liquid and stir, adding a certain amount of silicon sol at last more fully stirs and makes it even, formed behind the white jelly in 130-140 ℃ of following crystallization 4-7 days, take out the after scouring oven dry and remove template at 550 ℃ of roasting certain hours again, obtain having the composite zeolite molecular sieve of the two microvoid structures of Y/ β at last.
According to preparation method provided by the present invention, it is characterized in that preparation process carries out in the following order:
I uses water glass, sodium metaaluminate, the vitriol oil, water, sodium hydroxide to be raw material, in molar ratio (2-4) Na
2O: (3-8) SiO
2: Al
2O
3: (220-280) H
2The system proportioning of O, and add the directed agents of 3-4% (volume ratio) amount evenly is loaded on each mixing of materials in the stainless steel cauldron behind 80-90 ℃ of crystallization 20-30h, tentatively synthesizes Y zeolite;
II is dissolved in an amount of tetraethyl-amine bromide and uses a certain amount of distilled water, and adds a spot of ammoniacal liquor, mixes;
The y-type zeolite that III tentatively synthesizes I mixes with II solution after leaching supernatant liquid, and continues to stir;
IV adds a certain amount of silicon sol in III, if the higher available sulfuric acid of basicity regulates, be mixed into white jelly after, be loaded in the stainless steel cauldron in 130-140 ℃ of crystallization 4-7 days, take out after scouring to neutrality and dry again, obtain sample;
Sample after the V oven dry obtains the finished product in 550 ℃ of roasting 4-5h.
Four, description of drawings
The XRD diffractogram of Fig. 1 Y/ β double-micropore zeolites sieve sample
Five, embodiment
Embodiment 1
First with 70ml distilled water, the 2ml vitriol oil, 25ml sodium silicate solution ([SiO
2]=4.85mol/L, [OH]=2.75mol/L), 11.5ml sodium aluminate solution ([Al
2O
3]=2.09mol/L, [OH]=8.25mol/L), (its constitutive molar ratio is the 3ml directed agents: 16Na
2O: 15SiO
2: Al
2O
3: 320H
2O), after adding was mixed into jelly successively, in the 100ml stainless steel cauldron of packing into, 90 ℃ of following crystallization 27h took out, and it is stand-by tentatively to obtain y-type zeolite;
Then with 35ml distilled water, 15gTEABr (tetraethyl-amine bromide), 5mlNH
3.H
2O (strong aqua), the y-type zeolite that synthesizes earlier leaches supernatant liquid, 45ml silicon sol ([SiO
2]=6.05mol/L), adding divides in 3 the 50ml stainless steel cauldrons of packing into after being mixed into even white thing successively, takes out in 5 days in 140 ℃ of following crystallization, washs to dry after solution is neutrality, again with sample in 550 ℃ of roasting 5h, obtain Y/ β double-micropore zeolites sieve sample through XRD analysis.Spectrogram as shown in Figure 1.
First with 70ml distilled water, the 2ml vitriol oil, 25ml sodium silicate solution ([SiO
2]=4.85mol/L, [OH]=2.75mol/L), 11.5ml sodium aluminate solution ([Al
2O
3]=2.09mol/L, [OH]=8.25mol/L), (its constitutive molar ratio is the 3ml directed agents: 16Na
2O: 15SiO
2: Al
2O
3: 320H
2O), after adding was mixed into jelly successively, in the 100ml stainless steel cauldron of packing into, 90 ℃ of following crystallization 27h took out, and it is stand-by tentatively to obtain y-type zeolite;
Then with 35ml distilled water, 15gTEABr (tetraethyl-amine bromide), 5mlNH
3.H
2O (strong aqua), the y-type zeolite that synthesizes earlier leaches supernatant liquid, 45ml silicon sol ([SiO
2]=6.05mol/L), adding divides in 3 the 50ml stainless steel cauldrons of packing into after being mixed into even white thing successively, takes out in 6 days in 140 ℃ of following crystallization, washs to dry after solution is neutrality, again with sample in 550 ℃ of roasting 5h, obtain Y/ β double-micropore zeolites sieve sample through XRD analysis.
Embodiment 3
First with 70ml distilled water, the 2ml vitriol oil, 25ml sodium silicate solution ([SiO
2]=4.85mol/L, [OH]=2.75mol/L), 11.5ml sodium aluminate solution ([Al
2O
3]=2.09mol/L, [OH]=8.25mol/L), (its constitutive molar ratio is the 3ml directed agents: 16Na
2O: 15SiO
2: Al
2O
3: 320H
2O), after adding was mixed into jelly successively, in the 100ml stainless steel cauldron of packing into, 90 ℃ of following crystallization 27h took out, and it is stand-by tentatively to obtain y-type zeolite;
Then with 35ml distilled water, 15gTEABr (tetraethyl-amine bromide), 5mlNH
3.H
2O (strong aqua), the y-type zeolite that synthesizes earlier leaches supernatant liquid, 45ml silicon sol ([SiO
2]=6.05mol/L), adding divides in 3 the 50ml stainless steel cauldrons of packing into after being mixed into even white thing successively, takes out in 7 days in 140 ℃ of following crystallization, washs to dry after solution is neutrality, again with sample in 550 ℃ of roasting 5h, obtain the mixture of y-type zeolite and sodalite through XRD analysis.
Embodiment 4
First with 70ml distilled water, the 1.5ml vitriol oil, 25ml sodium silicate solution ([SiO
2]=4.85mol/L, [OH]=2.75mol/L), 1.5ml sodium aluminate solution ([Al
2O
3]=2.28mol/L, [OH]=8.96mol/L), (its constitutive molar ratio is the 3ml directed agents: 16Na
2O: 15SiO
2: Al
2O
3: 320H
2O), after adding was mixed into jelly successively, in the 100ml stainless steel cauldron of packing into, 90 ℃ of following crystallization 24h took out, and it is stand-by tentatively to obtain y-type zeolite;
Then with 30ml distilled water, 12gTEABr (tetraethyl-amine bromide), 5.5mlNH
3.H
2O (strong aqua), the y-type zeolite that synthesizes earlier leaches supernatant liquid, 42ml silicon sol ([SiO
2]=6.05mol/L), adding divides in 3 the 50ml stainless steel cauldrons of packing into after being mixed into even white thing successively, takes out in 3 days in 140 ℃ of following crystallization, washs to dry after solution is neutrality, again with sample in 550 ℃ of roasting 5h, obtain having only the sample of y-type zeolite molecular sieve through XRD analysis.
First with 70ml distilled water, the 1.5ml vitriol oil, 25ml sodium silicate solution ([SiO
2]=4.85mol/L, [OH]=2.75mol/L), 1.5ml sodium aluminate solution ([Al
2O
3]=2.28mol/L, [OH]=8.96mol/L), (its constitutive molar ratio is the 3ml directed agents: 16Na
2O: 15SiO
2: Al
2O
3: 320H
2O), after adding was mixed into jelly successively, in the 100ml stainless steel cauldron of packing into, 90 ℃ of following crystallization 24h took out, and it is stand-by tentatively to obtain y-type zeolite;
Then with 30ml distilled water, 12gTEABr (tetraethyl-amine bromide), 5.5mlNH
3.H
2O (strong aqua), the y-type zeolite that synthesizes earlier leaches supernatant liquid, 42ml silicon sol ([SiO
2]=6.05mol/L), adding divides in 3 the 50ml stainless steel cauldrons of packing into after being mixed into even white thing successively, takes out in 4 days in 140 ℃ of following crystallization, washs to dry after solution is neutrality, again with sample in 550 ℃ of roasting 5h, obtain Y/ β double-micropore zeolites sieve sample through XRD analysis.
Embodiment 6
First with 70ml distilled water, the 1.5ml vitriol oil, 25ml sodium silicate solution ([SiO
2]=4.85mol/L, [OH]=2.75mol/L), 10.5ml sodium aluminate solution ([Al
2O
3]=2.28mol/L, [OH]=8.96mol/L), (its constitutive molar ratio is the 3ml directed agents: 16Na
2O: 15SiO
2: Al
2O
3: 320H
2O), after adding was mixed into jelly successively, in the 100ml stainless steel cauldron of packing into, 90 ℃ of following crystallization 24h took out, and it is stand-by tentatively to obtain y-type zeolite;
Then with 30ml distilled water, 18gTEABr (tetraethyl-amine bromide), 5.5mlNH
3.H
2O (strong aqua), the y-type zeolite that synthesizes earlier leaches supernatant liquid, 45ml silicon sol ([SiO
2]=6.05mol/L), adding divides in 3 the 50ml stainless steel cauldrons of packing into after being mixed into even white thing successively, took out in 6 days in 140 ℃ of following crystallization, wash solution and be the oven dry of neutral back, again with sample in 550 ℃ of roasting 5h, obtain being mixed with the Y/ β double-micropore zeolites sieve sample of stray crystal through XRD analysis.
Embodiment 7
First with 280ml distilled water, the 5ml vitriol oil, 100ml sodium silicate solution ([SiO
2]=4.85mol/L, [OH]=2.75mol/L), 37.5ml sodium aluminate solution ([Al
2O
3]=2.56mol/L, [OH]=9.98mol/L), (its constitutive molar ratio is the 12ml directed agents: 16Na
2O: 15SiO
2: Al
2O
3: 320H
2O), after adding was mixed into jelly successively, in the 500ml stainless steel cauldron of packing into, 90 ℃ of following crystallization 25h took out, and it is stand-by tentatively to obtain y-type zeolite;
Then with 100ml distilled water, 45gTEABr (tetraethyl-amine bromide), 15mlNH
3H
2O (strong aqua), the y-type zeolite that synthesizes earlier leaches supernatant liquid, 70ml silicon sol ([SiO
2]=6.05mol/L), adding divides in the 500ml stainless steel cauldron of packing into after being mixed into even white thing successively, takes out in 5 days in 140 ℃ of following crystallization, washs to dry after solution is neutrality, again with sample in 550 ℃ of roasting 5h, obtain β+P type zeolite molecular sieve sample through XRD analysis.
Embodiment 8
First with 70ml distilled water, the 2ml vitriol oil, 25ml sodium silicate solution ([SiO
2]=4.85mol/L, [OH]=2.75mol/L), 11.5ml sodium aluminate solution ([Al
2O
3]=2.09mol/L, [OH]=8.25mol/L), (its constitutive molar ratio is the 3ml directed agents: 16Na
2O: 15SiO
2: Al
2O
3: 320H
2O), after adding was mixed into jelly successively, in the 100ml stainless steel cauldron of packing into, 90 ℃ of following crystallization 27h took out, and it is stand-by tentatively to obtain y-type zeolite;
Then with 30ml distilled water, 18gTEABr (tetraethyl-amine bromide), 5mlNH
3.H
2O (strong aqua), the y-type zeolite that synthesizes earlier leaches supernatant liquid, 45ml silicon sol ([SiO
2]=6.05mol/L), adding divides in 3 the 50ml stainless steel cauldrons of packing into after being mixed into even white thing successively, takes out in 8 days in 140 ℃ of following crystallization, washs to dry after solution is neutrality, again with sample in 550 ℃ of roasting 5h, obtain having only the zeolite molecular sieve sample of beta structure through XRD analysis.
Claims (4)
1. the double-micropore zeolites molecular sieve is characterized in that it being a kind of Y/ β double-micropore zeolites material, has pore passage structure and the crystalline structure of Y and β.
2. claim 1 is described. the preparation method of double-micropore zeolites molecular sieve, it is characterized in that it being a kind of method of synthetic Y/ β double-micropore zeolites molecular sieve, and described method step is in the following order carried out:
I uses water glass, sodium metaaluminate, the vitriol oil, water, sodium hydroxide to be raw material, in molar ratio (2-4) Na
2O: (3-8) SiO
2: Al
2O
3: (220-280) H
2The system proportioning of O, and add the directed agents of 3-4% (volume) amount evenly is loaded on each mixing of materials in the stainless steel cauldron behind 80-90 ℃ of crystallization 20-30h, tentatively synthesizes Y zeolite;
II is dissolved in an amount of tetraethyl-amine bromide and uses a certain amount of distilled water, and adds a spot of ammoniacal liquor, mixes;
The y-type zeolite that III tentatively synthesizes I mixes with II solution after leaching supernatant liquid, and continues to stir;
IV adds a certain amount of silicon sol in III, be mixed into white jelly after, finally be (1.5-3.0) Na in molar ratio
2O: (10-30) SiO
2: Al
2O
3: (1.0-5.0) (TEA)
2O: (200-360) H
2The system proportioning of O is loaded in the stainless steel cauldron in 130-140 ℃ of crystallization 4-7 days if the higher available sulfuric acid of basicity is regulated, and takes out after scouring to neutrality and dries, obtains sample;
Sample after V will be dried obtains the finished product in 550 ℃ of roasting 4-5h.
3. described according to claim 2. the preparation method of double-micropore zeolites molecular sieve is characterized in that the mole ratio range of each material in the used directed agents is: (13.0-16.0) Na
2O: (12-18) SiO
2: Al
2O
3: (300-350) H
2O.
4. according to the preparation method of the described double-micropore zeolites molecular sieve of claim 2., it is characterized in that the relative content of y-type zeolite and zeolite beta can be regulated by the consumption or the reaction times of tetraethyl-amine bromide and silicon sol in the prepared product, the percentage composition of y-type zeolite is 0-100% in the two micropore composite zeolites of Y/ β.
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